Phosphine-Catalyzed Activation of Phenylsilane for Benzaldehyde Reduction

Hydrosilylation reactions are commonly used for the reduction of carbonyl bonds in fine chemistry, catalyzed by transition metal complexes. The current challenge is to expand the scope of metal-free alternative catalysts, including in particular organocatalysts. This work describes the organocatalyzed hydrosilylation of benzaldehyde with a phosphine, introduced at 10 mol%, and phenylsilane at room temperature. The activation of phenylsilane was highly dependent on the physical properties of the solvent such as the polarity, and the highest conversions were obtained in acetonitrile and propylene carbonate with yields of 46 % and 97 %, respectively. The best results of the screening over 13 phosphines and phosphites were obtained with linear trialkylphoshines (PMe₃ , Pⁿ Bu₃ , POct₃ ), indicating the importance of their nucleophilicity, with yields of 88 %, 46 % and 56 %, respectively. With the help of heteronuclear ¹ H-²⁹ Si NMR spectroscopy, the products of the hydrosilylation (PhSiH_3-n (OBn)_n ) were identified, allowing a monitoring of the concentration in the different species, and thereby of their reactivity. The reaction displayed an induction period of ca. 60 min, followed by the sequential hydrosilylations presenting various reaction rates. In agreement with the formation of partial charges in the intermediate state, we propose a mechanism based on a hypervalent silicon center via the Lewis base activation of the silicon Lewis acid.